In order to shorten the process of textile printing with natural dyes, develop new methods, and improve the color fastness and quality of printed products, this study presents a novel approach by synthesizing a natural complex dye through the interaction between purpurin and Fe2+ ions, resulting in a compound named purpurin–Fe2+ (P-Fe). This synthesized complex dye was meticulously characterized using state-of-the-art analytical techniques, including Fourier transform infrared spectroscopy (FT-IR), ultraviolet–visible (UV–Vis) spectrophotometry, and scanning electron microscopy energy-dispersive spectroscopy (EDS). The characterization confirmed the successful complexation of purpurin with Fe2+ ions. The prepared complex dye P-Fe was used for the printing of silk fabric. The optimized printing process involves steaming at a temperature of 100 °C for a duration of 20 min. In comparison to fabrics printed using direct dyes, the K/S values of the fabric printed with the P-Fe complex showed a significant enhancement, with all color fastness ratings achieving grade four. Furthermore, the proportion of metal elements on the white background of the printed fabric was found to be less than 0.180%, and the level of whiteness was above 50. The application of the P-Fe dye in silk fabric printing not only streamlines the printing process but also enhances the depth and speed of the printed color, effectively addressing the issue of color transfer onto a white background, which is commonly associated with natural dyes.